JP6821570B2 - Polycondensation product containing a phenolic copolymer and a dispersant for a hydraulic composition containing the same. - Google Patents

Description

The present invention relates to a polycondensation product containing a novel phenolic copolymer. More specifically, the present invention relates to a polycondensation product obtained by copolymerizing a monomer mixture containing an alkylene oxide adduct of hydroxyethylphenol, a derivative of the alkylene oxide adduct of phenol, and aldehydes.

In recent years, as aggregates as concrete materials, there are increasing opportunities to use low-quality aggregates that have not been actively used in the past due to the depletion of high-quality fine aggregates such as river sand. .. A hydraulic composition using such a low-quality fine aggregate tends to have a high viscosity at the time of freshness and a decrease in workability even at a general water powder ratio (W / B). .. Such a problem is likely to occur especially when the amount of impurities (eg, clay, etc.) contained in the aggregate is large.
Further, since the aggregate used as a material for a hydraulic composition is a natural product, the content of impurities varies. Therefore, when a conventional polycarboxylic acid-based dispersant is used, the amount of the dispersant required to obtain a certain fluidity varies depending on the type of aggregate used and its origin, and thus water. In the actual production of the rigid composition, it is necessary to adjust the amount of the dispersant used each time, which makes various operations complicated. In addition, when a large amount of the above-mentioned low-quality aggregate is used, it is often necessary to increase the amount of the dispersant added in order to secure a certain fluidity, which causes an increase in manufacturing cost. ..

To solve such problems, the fluidity is improved by a method of using a conventional polycarboxylic acid-based dispersant in combination with other components, or a method of optimizing the structure of the polycarboxylic acid-based dispersant itself. , Several prior art examples are disclosed that enhance the effectiveness as a polycarboxylic acid-based water reducing agent.
As an example of the combined use of the above-mentioned other components, when using a low-quality aggregate containing a swellable clay (for example, smectite, montmorillonite, etc.), a substance containing an inorganic cation as a clay activity-altering substance (for example, for example). EO / PO plasticizers (ie, polycarboxylic acid-based water reducing agents) for substances containing organic cations (eg, tetrabutylammonium bromide, etc.) and polar organic molecules (eg, polyethylene glycol, sodium hexametaphosphate, etc.) There is a proposal to improve the effectiveness of a polycarboxylic acid-based water reducing agent by using it in combination with (Patent Document 1). In addition, when using fine aggregates of low quality, a cationic polymer containing quaternary nitrogen (for example, poly (diallyldimethylammonium) salt, etc.) is used as a high-performance water reducing agent or a high-performance AE water reducing agent (polycarboxylic acid-based water reducing agent). A proposal to improve the fresh state such as concrete viscosity and flow retention by using it in combination with an agent (Patent Document 2). When a clay-containing aggregate is used, a poly-cationic compound (for example, polydiallyldimethylammonium) By using a poly-hydroxyl or hydroxyl carboxylate component (for example, sodium gluconate, etc.) in combination with a polycarboxylate-based dispersant, the dispersant has undergone improvement in maintaining the dose efficiency exhibited in cement mortar. There is a proposal (Patent Document 3).
Furthermore, as a proposal to improve the structure of the polycarboxylic acid-based dispersant itself, a comb-shaped copolymer containing a main hydrocarbon chain and a side chain containing a gem-bisphosphonate group in addition to a carboxy group and a polyoxyalkylene group is used as mineral particles. There is a proposal (Patent Document 4) that has improved the fluidity of the suspension by adopting it as a fluidizing agent for the suspension.

Japanese Patent No. 4491078 Japanese Patent No. 4381923 Japanese Unexamined Patent Publication No. 2011-136844 Japanese Patent No. 5623672

However, the proposals so far have not achieved satisfactory fluidity without being significantly affected by the type of aggregate used and the amount of impurities.
Therefore, with the transition of aggregates used, there is a demand for a new dispersant for hydraulic compositions that can exhibit a certain fluidity with almost no change in the amount of aggregate added, regardless of the quality of the aggregates. ..
On the other hand, there has been no proposal to use an alkylene oxide adduct of hydroxyethylphenol as a raw material for an additive for a hydraulic composition.

The present invention has been made to improve the performance of a dispersant for a hydraulic composition under the background of the prior art, and has stable dispersibility regardless of the content of impurities in the aggregate. Contains a dispersant for hydraulic compositions that can obtain a predetermined fluidity without substantially changing the amount added depending on the type of aggregate, and a novel phenolic copolymer useful as a dispersant for such hydraulic compositions. It is an object of the present invention to provide a polycondensation product.

As a result of diligent studies by the present inventors, the alkylene oxide adduct of hydroxyethylphenol, which has not been studied as a material for additives for water-hard composition, is used as a monomer of a polycondensation product containing a phenol-based copolymer. By using as a component, i.e., structural units derived from the alkylene oxide adduct of hydroxyethylphenol are incorporated into the structure of the copolymer, and the copolymer or polycondensation product containing it is added for a water-hard composition. We have found that by using it as an agent, it is possible to provide a water-hard composition having a desired fluidity regardless of the type and amount of impurities such as clay that can be contained in the aggregate, and completed the present invention.

（式中、
Ａ_１Ｏ及びＡ_２Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキサイド基を表し、
ｍ及びｎは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｍ＋ｎ≧１であり、
Ａ_３Ｏは炭素原子数２乃至４のアルキレンオキサイド基を表し、
ｐはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、
Ｘは水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数２乃至２４のアシル基を表し、
Ａ_４Ｏは炭素原子数２乃至４のアルキレンオキサイド基を表し、
ｑはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、
Ｒ_０は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、
Ｒ_１は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、
Ｙ_１及びＹ_２はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表し、
Ｙ_３はリン酸エステル基又は硫酸エステル基を表し、
Ｒ_２は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、
ｒは１乃至１００の数を表す。）That is, the present invention includes compound A represented by the following formula (A), compound B represented by the formula (B), compound C represented by the formula (C), and one or more kinds represented by the formula (D). The present invention relates to a polycondensation product, which comprises a copolymer obtained by polycondensing a monomer mixture containing an aldehyde compound D.

(During the ceremony,
A ₁ O and A ₂ O each independently represent an alkylene oxide group having 2 to 4 carbon atoms.
m and n are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, and m + n ≧ 1.
A ₃ O represents an alkylene oxide group having 2 to 4 carbon atoms.
p is the average number of moles of alkylene oxide added and represents a number from 1 to 300.
X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.
A 4 _O represents an alkylene oxide group having 2 to 4 carbon atoms,
q is the average number of moles of alkylene oxide added and represents a number from 1 to 300.
R ₀ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms.
R ₁ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms.
Y ₁ and Y ₂ independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group, respectively.
Y ₃ represents a phosphoric acid ester group or a sulfuric acid ester group,
R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group,
r represents a number from 1 to 100. )

In the monomer mixture, the polycondensation product contains the compound A, the compound B and the compound C in a molar ratio of compound A: compound B: compound C = 0.1 to 2: 0.1 to 2: 1. Compound D is contained in a ratio of 0.1 to 4 and compound D is contained in a molar ratio with respect to the total molar amount of the compound A, the compound B and the compound C (Compound A + Compound B + Compound C): Compound D = It is preferably contained in a ratio of 1 to 10: 10 to 1.
Further, the polycondensation product may contain a compound B represented by two or more kinds of formulas (B) in the monomer mixture, and further represented by two or more kinds of formulas (C). It may contain compound C.

Furthermore, the present invention also relates to a dispersant for a hydraulic composition containing the above-mentioned polycondensation product or copolymer.

The present invention is represented by the compound A represented by the formula (A), the compound B represented by the formula (B), the compound C represented by the formula (C), and the compound C represented by the formula (D). Copolymers obtained by polycondensing a monomer mixture containing one or more aldehyde compounds D are also targeted.

INDUSTRIAL APPLICABILITY According to the present invention, excellent dispersion stability can be exhibited with respect to a hydraulic composition without significantly changing the addition amount regardless of the type of impurities in the aggregate and the amount thereof, and not only that. Water with high water reduction, shortening of kneading time until the hydraulic composition is put into a fluid state, good stability over time, low concrete viscosity, and low setting delay. It is possible to provide a dispersant for a rigid composition, a phenolic copolymer preferably used as the dispersant, and a polycondensation product containing the same.

The polycondensation product containing the above-mentioned copolymer of the present invention can also reduce the unfavorable influence that can be caused by the presence of carbon content, typically unburned carbon, contained therein in the hydraulic composition. It has the effect of being able to do it. That is, the polycondensation product or copolymer of the present invention can maintain a high water-reducing state even when it is blended in a concrete composition containing fly ash (FA) as a dispersant for a hydraulic composition. In particular, in the cured product of the FA compound composition, it is possible to suppress the generation of darkening of the surface caused by the floating of unburned carbon on the surface of concrete, and it is possible to provide a cured product having an excellent appearance.

As described above, the polycondensation product or copolymer of the present invention is a water-hard composition capable of suppressing deterioration of the fluidity of the water-hard composition, which is a concern when impurities such as clay such as clay and bentonite are present. A polycondensation product or copolymer useful as an additive for use.
In the hydraulic composition to which the polycondensation product or copolymer of the present invention is applied, impurities include clay and clay.
In the present specification, clay refers to collected fine particles defined as a metal sieve having a nominal size of 75 μm defined by JIS Z 8801-1.
Further, in the present specification, clay includes not only clay minerals having a layered structure but also clay minerals having no layered structure such as imogolite and allophane. Clay minerals with a layered structure include swelling minerals such as smectite, vermiculite, montmorillonite, bentonite, illite, hectrite, halloysite, mica, and brittle mica; kaolin mineral (kaolinite), serpentine, pyrophyllite, talc, and black. Examples include non-swelling minerals such as light.

Further, the polycondensation product or copolymer of the present invention is suitably used in hydraulic compositions as an additive for hydraulic compositions, and in particular, coal ash such as fly ash, cinder ash, slag ash, and bottom ash. , Silica fume, silica dust, molten silica fine powder, blast furnace slag, volcanic ash, silicic acid white clay, diatomaceous soil, metacaolin, silica sol, precipitated silica and other pozzolanic fine powders are also suitably used for hydraulic compositions.

<Polycondensation product and copolymer>
The present invention relates to an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof (Compound A), an alkylene oxide adduct of phenol or a derivative thereof (Compound B), a phosphoric acid ester or a sulfuric acid ester derivative of the alkylene oxide adduct of phenol (Compound A). C), a polycondensation product containing a copolymer obtained by copolymerizing a monomer mixture containing aldehydes (Compound D), and the copolymer are targeted.
In the present invention, the term "polycondensation product containing a copolymer obtained by polycondensing a monomer mixture" is used.
(1) An embodiment containing a copolymer (copolymer 1) in which all the components of the monomer mixture, that is, all of the compounds A to D are polycondensed.
(2) An embodiment comprising a copolymer (copolymer 2) in which one or two of compounds A to C and compound D are polycondensed in the monomer mixture.
(3) An embodiment containing the two types of copolymers (copolymer 1 and copolymer 2) of the above (1) and (2), and (4) the common weight of the above (1) and / or (2). A mode in which at least one of unreacted compounds A to D is contained in addition to the coalescence (copolymer 1 and / or copolymer 2).
In addition to including any of the above, in general, unreacted components generated in each polymerization step and each component (compound A to D) preparation step, for example, an alkylene oxide addition step, and components including side reactants are also included. Has been done.
Hereinafter, the compounds A to D contained in the monomer mixture will be described in detail.

式中、Ａ_１Ｏ及びＡ_２Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキサイド基を表し、ｍ及びｎはアルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｍ＋ｎ≧１である。
またＹ_１及びＹ_２はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表す。[Compound A represented by the formula (A)]
Compound A is an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof, and has a structure represented by the following formula (A).

In the formula, A ₁ O and A ₂ O each independently represent an alkylene oxide group having 2 to 4 carbon atoms, and m and n are the average number of moles of alkylene oxide added, respectively, and 0 to 0 to n respectively. It represents a number of 300 and m + n ≧ 1.
Further, Y ₁ and Y ₂ independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group, respectively.

The compound A is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to at least one or both of a hydroxyethyl group and a phenolic hydroxy group with respect to hydroxyethylphenol, and the alkylene Derivatives of the oxide adduct (phosphate or sulfate) are also included in Compound A.
The hydroxyethylphenol may be any of o-hydroxyethyl-phenol, m-hydroxyethyl-phenol, and p-hydroxyethyl-phenol. Compound A is preferably a compound (and an ester derivative thereof) in which alkylene oxide having 2 to 4 carbon atoms is added to o-hydroxyethyl-phenol.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides can be added alone or mixed, and when two or more kinds of alkylene oxides are used, they can be added. Either block addition or random addition may be used.

That is, examples of the alkylene oxide group having 2 to 4 carbon atoms in A ₁ O and A ₂ O include an ethylene oxide group, a propylene oxide group and a butylene oxide group. A ₁ O and A ₂ O may be composed of only an ethylene oxide group, a propylene oxide group or a butylene oxide group, or may contain two or more of these groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
Further, m and n are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, preferably 0 to 60, and m + n ≧ 1. By increasing the number of moles of A ₁ O _and A ₂ O added, improvement in water reduction can be expected.

When Y ₁ and Y ₂ represent a phosphoric acid ester group, they are a phosphoric acid monoester and / or a salt thereof, a phosphoric acid diester and / or a salt thereof, or a phosphoric acid triester, or a mixture thereof. _{When 1} , Y ₂ represents a sulfate ester group, they are a sulfate monoester and / or a salt thereof, or a sulfate diester, or a mixture thereof.
Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.
By anionizing the terminal of compound A, that is, by making it a phosphate ester or a sulfate ester derivative, the kneading time of the mortar can be shortened when added to the hydraulic composition.

The compound A represented by the above formula (A) can be used alone or in combination of two or more.

上記式中、Ａ_３Ｏは炭素原子数２乃至４のアルキレンオキサイド基を表し、ｐはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、Ｒ_０は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、Ｘは水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数２乃至２４のアシル基を表す。[Compound B represented by the formula (B)]
Compound B is an alkylene oxide adduct of phenol or a derivative thereof, and has a structure represented by the following formula (B).

In the above formula, A 3 _O represents an alkylene oxide group having 2 to 4 carbon atoms, p is a number from 1 to 300 an average molar number of addition of alkylene oxide, R ₀ is a hydrogen atom, the number of carbon atoms It represents an alkyl group of 1 to 24 or an alkenyl group having 2 to 24 carbon atoms, and X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.

The compound B is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenol or a substitute thereof, and a derivative (alkyl ester or fatty acid ester) of the alkylene oxide adduct is also included in the compound B. Ru.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides can be added alone or mixed, and when two or more kinds of alkylene oxides are used, they can be added. Either block addition or random addition may be used.

That is, as the alkylene oxide group of the A ₃ carbon atoms in the _O 2 to 4, ethylene oxide groups, propylene oxide groups, and butylene oxide groups. A 3 _O is an ethylene oxide group, may be composed of only propylene oxide groups or butylene oxide groups, may contain two or more of them in groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
The p is an average molar number of addition of alkylene oxide, 1 to 300, preferably a number from 1 to 150, by increasing the addition number of moles of A 3 _O, it can be expected to improve the water-reducing properties.

Examples of the alkyl group having 1 to 24 carbon atoms in R ₀ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl. Group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, dodecyl group (lauryl group), tetradecyl group (milstyl group), Examples thereof include a hexadecyl group (palmityl group), an octadecyl group (stearyl group), an icosyl group, a docosyl group (behenyl group), a tetracosyl group, and the like, which may have a branched structure or a cyclic structure.
Further, examples of the alkenyl group having 2 to 24 carbon atoms include a group having one carbon-carbon double bond in the alkyl group having 1 to 24 carbon atoms. Specifically, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, docosenyl group, Examples thereof include a tetracosenyl group, which may have a branched structure or a cyclic structure.
In compound B, when R ₀ is an alkyl group having 1 to 24 carbon atoms (an alkyl substituent is used), fly ash (FA) is blended as a hydraulic powder in the hydraulic composition. The fluidity is improved, the occurrence of darkening on the surface of the cured product obtained from the FA-blended hydraulic composition can be suppressed, and by further lengthening the carbon chain of _R0 , the cured product obtained from the FA-blended hydraulic composition can be suppressed. It can be expected that the appearance will be better.

The alkyl group having 1 to 10 carbon atoms in X may have a branched structure or a cyclic structure, and specific examples thereof include an alkyl group having 1 to 24 carbon atoms in R ₀ . Among the groups, alkyl groups having 1 to 10 carbon atoms can be mentioned.
Examples of the acyl group having 2 to 24 carbon atoms include a saturated or unsaturated acyl group (R'(CO) -group, R'is a hydrocarbon group having 1 to 23 carbon atoms). For example, saturated acyl groups having 2 to 24 carbon atoms include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanic acid, octanoic acid (capric acid), nonanoic acid and decanoic acid ( Capric acid), dodecanoic acid (lauric acid), tetradecanoic (myristic acid), pentadecanoic acid (pentadecic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecan acid, eikosan Acrylic groups derived from carboxylic acids and fatty acids such as acids (arachidic acid), docosanoic acid (bechenic acid) and tetracosanoic acid (lignoseric acid), and monounsaturated acyl groups include myristoleic acid, palmitenic acid, oleic acid, Acrylic groups derived from monounsaturated fatty acids such as ellaic acid, baxenoic acid, gadrainic acid, eicosenoic acid, erucic acid, and nervonic acid are diunsaturated acyl groups, and diunsaturated acyl groups include linoleic acid, eikosazienoic acid, and docosazienoic acid. Acrylic groups derived from saturated fatty acids, and as triunsaturated acyl groups, triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, meadic acid, dihomo-γ-linolenic acid, and eikosatrienic acid. Examples include the derived acyl group.
Further, preferable X includes a hydrogen atom and an acetyl group.

The compound B represented by the above formula (B) can be used alone or in combination of two or more. By using two or more kinds of compounds as compound B in combination in the monomer mixture described later, the effect of improving the retention rate of mortar flow can be expected.

式中、Ａ_４Ｏは炭素原子数２乃至４のアルキレンオキサイド基を表し、ｑはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、Ｒ_１は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、Ｙ_３はリン酸エステル基又は硫酸エステル基を表す。[Compound C represented by the formula (C)]
Compound C is a phosphoric acid ester or sulfate ester derivative of an alkylene oxide adduct of phenol, and has a structure represented by the following formula (C).

In the formula, A ₄ O represents an alkylene oxide group having 2 to 4 carbon atoms, q represents the average number of moles of alkylene oxide added and represents 1 to 300, and R ₁ is a hydrogen atom and 1 carbon atom. or an alkyl group, or an alkenyl group having a carbon number of 2 to 24 24, Y ₃ represents a phosphoric acid ester group or a sulfuric acid ester group.

The compound C is a phosphate ester or sulfate ester derivative of a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenol or a substitute thereof.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides can be added alone or mixed, and when two or more kinds of alkylene oxides are used, they can be added. Either block addition or random addition may be used.

That is, as the alkylene oxide group of the A ₄ carbon atoms in the _O 2 to 4, ethylene oxide groups, propylene oxide groups, and butylene oxide groups. A 4 _O is an ethylene oxide group, may be composed of only propylene oxide groups or butylene oxide groups, may contain two or more of them in groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
Further, q is the average number of moles of alkylene oxide added, and represents a number of 1 to 300, preferably 1 to 40.

Specific examples of the alkenyl groups of the alkyl group and the carbon atoms 2 to 24 carbon atoms having 1 to 24 in the R _1, specific examples of R ₀ in the description of the compounds B and the like.
In addition, also in the case of compound C, when fly ash (FA) is blended as a hydraulic powder in a hydraulic composition by using R ₁ as an alkyl group having 1 to 24 carbon atoms (as an alkyl substituent). The fluidity in the FA-blended hydraulic composition is improved, the occurrence of darkening on the surface of the cured product obtained from the FA-blended hydraulic composition can be suppressed, and by further lengthening the carbon chain of R ₁ , the cured product obtained from the FA-blended hydraulic composition can be suppressed. It can be expected that the appearance of the product will be improved.

If Y ₃ represents a phosphate ester group, they are a phosphate monoester and / or a salt thereof, a phosphate diester and / or a salt thereof, or a phosphate triester, or a mixture thereof, and Y ₃ is a sulfate. When representing ester groups, they are sulfate monoesters and / or salts thereof, or sulfate diesters, or mixtures thereof.
Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.

As the compound C represented by the above formula (C), a compound represented by the following formula can be mentioned.
In the formula, R ₁ , A ₄ O, and q represent the same as those defined in the above formula (C), and Ph represents a phenylene group. Further, M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as calcium or magnesium; an ammonium group; an organic ammonium group such as an alkylammonium group or an alkanolammonium group.
Further, Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R "-O- (A'O) s- (in the formula, R" represents an alkyl group having 1 to 24 carbon atoms, and A'. O represents an oxyalkylene group having 2 to 3 carbon atoms, that is, an oxyethylene group or an oxypropylene group, and s is the average number of moles of the oxyalkylene group A'O, which represents 1 to 100). Representing, when a plurality of Z's are present, they may be the same group or different groups.
-Phosphoric acid monoester and its salt R _1- Ph-O- [A ₄ O] q-P (= O) (-OM) ₂
-Phosphoric acid diester and its salt [R _1- Ph-O- [A ₄ O] q-] ₂ P (= O) (-OM)
[R _1- Ph-O- [A ₄ O] q-] (Z-) P (= O) (-OM)
-Phosphate triester [R _1- Ph-O- [A ₄ O] q-] ₃ P (= O)
[R _1- Ph-O- [A ₄ O] q-] ₂ (Z-) P (= O)
[R _1- Ph-O- [A ₄ O] q-] (Z-) ₂ P (= O)
-Sulfuric acid monoester and its salt R _1- Ph-O- [A ₄ O] q-S (= O) ₂ (-OM)
-Sulfuric acid diester [R _1- Ph-O- [A ₄ O] q-] ₂ S (= O) ₂
[R _1- Ph-O- [A ₄ O] q-] (Z-) S (= O) ₂

The compound C represented by the above formula (C) can be used alone or in combination of two or more.

上記式中、Ｒ_２は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、ｒは１乃至１００の数を表す。
なおこれらアルキル基、アルケニル基、フェニル基、ナフチル基及びヘテロ環式基は、炭素原子数１乃至１０のアルキル基；フェニル基、ナフチル基等のアリール基；塩素原子、臭素原子等のハロゲン原子；スルホ基、スルホン酸塩基等のスルホン酸官能基；アセチル基等のアシル基；ヒドロキシ基；アミノ基；カルボキシル基等の任意の置換基で置換されていてもよい。[Aldehyde compound D represented by the formula (D)]
Compound D is an aldehyde and has a structure represented by the following formula (D).

In the above formula, R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group, and r is 1 to 1 to Represents a number of 100.
The alkyl group, alkenyl group, phenyl group, naphthyl group and heterocyclic group are alkyl groups having 1 to 10 carbon atoms; aryl groups such as phenyl group and naphthyl group; halogen atoms such as chlorine atom and bromine atom; It may be substituted with an arbitrary substituent such as a sulfonic acid functional group such as a sulfo group or a sulfonic acid base; an acyl group such as an acetyl group; a hydroxy group; an amino group; or a carboxyl group.

The alkyl group having 1 to 10 carbon atoms in R ₂ may have a branched structure or a cyclic structure, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a cyclopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1- Examples include adamantyl groups.
The alkenyl group having 2 to 10 carbon atoms may have a branched structure or a cyclic structure, and specifically, a vinyl group, a propenyl group, a butenyl group, a pentanyl group, a hexenyl group, a heptenyl group, a nonenyl group. , Desenel group and the like.
Further, examples of the heterocyclic group include a frill group, a thienyl group, a pyridyl group, a piperidyl group, a morpholino group and the like.
Further, r preferably represents a number of 2 to 100.

Compound D includes, for example, formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, barrelaldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, Dodecanal, achlorein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde, benzylaldehyde [(C ₆ H ₅ ) ₂ C (OH) -CHO ], Naftaldehyde, furfural, etc., among which can be selected from the group consisting of formaldehyde, paraformaldehyde, benzaldehyde or any mixture of two or more thereof.
Compound D can be used as a pure crystalline or powdery substance, or as a hydrate thereof, and can also be used in the form of an aqueous solution such as formalin, in which case the metering or mixing of the components is simplified. Can be done.

The compound D represented by the above formula (D) can be used alone or in combination of two or more.

[Monomer mixture]
In the monomer mixture containing the above compounds A to D used in the polycondensation product of the present invention, the mixing ratio thereof is not particularly limited, but preferably, the above compounds A, B and C are mixed in molar ratio. Compound A: Compound B: Compound C = 0.1 to 2: 0.1 to 2: 0.1 to 4 and with respect to the total molar amount of Compound A, Compound B and Compound C. , Compound D is preferably contained in a molar ratio of (Compound A + Compound B + Compound C): Compound D = 1 to 10: 10 to 1.
More preferably, Compound A: Compound B: Compound C = 0.1 to 1.0: 0.5 to 1.5: 0.5 to 3.5 (molar ratio), and (Compound A + Compound B + Compound C). ): Compound D = 2 to 6: 10 to 1 (molar ratio).
When the compounding ratio of compound A is increased in the monomer mixture, fluidity can be ensured even when impurities such as clay are mixed in the hydraulic composition, and the setting time can be expected to be shortened. Further, by adjusting the blending ratio of compound C, the water reduction and retention of the hydraulic composition can be adjusted.

[Copolymer and polycondensation product]
The polycondensation product of the present invention comprises a copolymer obtained by polycondensing a monomer mixture containing the above compounds A to D.
In obtaining the above-mentioned copolymer, the method for producing the compounds A to D and the polymerization method for obtaining the copolymer are not particularly limited.
Further, in the case of polycondensation, the order of addition and the method of addition of the above compounds A, B, C and D are not particularly limited. For example, the total amount of compounds A to D is collectively added before the polycondensation reaction. A part of Compound A to Compound D is added before the condensation reaction, and then the rest is divided and added by dropping, or a part of Compound A to Compound D is added before the polycondensation reaction, and the reaction time is constant. The rest after the lapse may be additionally added, or the like.

The polycondensation product comprises, for example, compound A, compound B, compound C and compound D in the presence of a dehydration catalyst, in the presence of a dehydration catalyst, in the absence of a solvent or in a solvent, at a reaction temperature of 80 ° C. to 150 ° C., under normal pressure to pressure. For example, it is obtained by polycondensing at 0.001 to 1 MPa.
Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitrate, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, and dimethyl sulfate. Phosic acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvate, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfon Examples thereof include acids, fluoroacetic acids, thioglycolic acids, mercaptopropionic acids, active white clay, etc. These dehydration catalysts can be used alone or in combination of two or more, and a polycondensation reaction is carried out under a solvent. In this case, water, a glycol ether compound such as propylene glycol monomethyl ether (PGME), an aromatic compound such as toluene or xylene, a cyclic aliphatic compound such as methylcyclohexane, or the like can be used as the solvent. Applicable as a dehydration catalyst (acid catalyst), for example, acetic acid can also be used as a solvent.
The reaction temperature can be preferably carried out at a temperature of 95 ° C. to 130 ° C., and the polycondensation reaction can be completed by reacting for 3 to 25 hours.
The polycondensation reaction is preferably carried out under acidic conditions, and the pH of the reaction system is preferably 4 or less.

Further, in addition to Compound A, Compound B, Compound C and Compound D, other monomers that can be polycondensed with these compounds may be added to the monomer mixture as long as the effects of the present invention are not impaired.
Other monomers include cresol, catechol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A, aniline, methylaniline, hydroxyaniline, methoxyaniline and / or salicylic acid, and 1 to 300 mol of alkylene. Additives with oxides, phenol, phenoxyacetic acid, methoxyphenol, resorcinol, cresol, bisphenol A, nonylphenol, aniline, methylaniline, N-phenyldiethanolamine, N, N-di (carboxyethyl) aniline, N, N-di ( Carboxymethyl) aniline, phenol sulfonic acid, anthranyl acid and the like can be mentioned.

After the completion of the polycondensation reaction, various conventionally known methods can be adopted in order to reduce the content of the unreacted aldehyde component (Compound D) in the reaction system. For example, a method in which the pH of the reaction system is alkaline and heat treatment is performed at 60 to 140 ° C., a method in which the reaction system is reduced in pressure (-0.1 to -0.001 MPa) to volatilize and remove the aldehyde component, and a small amount of sulfite. Examples thereof include a method of adding sodium hydrogen hydrogen, ethylene urea and / or polyethyleneimine.
The dehydration catalyst used in the reaction can be neutralized after the reaction is completed and removed by filtration in the form of a salt, but even in the embodiment in which the catalyst is not removed, the dispersion for the water-hard composition of the present invention described later will be described. The performance as an agent is not impaired. In addition to the above filtration, methods for removing the catalyst include phase separation, dialysis, ultrafiltration, and the use of an ion exchanger.
By neutralizing the reaction product and diluting it with water or the like, workability such as weighing in use as a dispersant for a hydraulic composition described later is improved. At this time, the basic compounds used for neutralization include alkaline hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, monoethanolamine, diethanolamine, and triethanolamine. Organic amines such as, etc. are mentioned, and one or a combination of two or more of them is adopted.

The finally obtained copolymer of the present invention in the range of 5,000 to 100,000 in terms of weight average molecular weight (gel permeation chromatography method (hereinafter referred to as "GPC method"), polyethylene glycol equivalent) is suitable. More preferably, the weight average molecular weight is in the range of 10,000 to 80,000, particularly preferably in the range of 15,000 to 35,000 in order to exhibit excellent dispersion performance.
As described above, the "polycondensation product" in the present invention may consist only of a copolymer obtained by polycondensing a monomer mixture containing compounds A to D, but in general, each of them may be used. Unreacted components generated in the polymerization step, alkylene oxide addition step, etc., and components including by-reactants are also included.

<Use of polycondensation products and copolymers>
The polycondensation product and copolymer of the present invention can widely exhibit their performance as a dispersant in an aqueous dispersion of various solid powders. Further, the polycondensation product and the copolymer of the present invention can be used as they are (without adding anything) as the above-mentioned dispersant, and publicly known and publicly available additives are appropriately adopted depending on various uses. It can also be used in the form of an admixture combined with the above.

<Dispersant for hydraulic composition>
Among the above applications, it can be particularly preferably used as a form of a dispersant for a hydraulic composition containing the above polycondensation product or copolymer.
The hydraulic composition refers to a composition containing a powder having physical properties that hardens by a hydration reaction (hydraulic powder), such as cement, gypsum, and fly ash. When the hydraulic powder is cement, the hydraulic composition is also referred to as a cement composition.

The dispersant for a hydraulic composition of the present invention can also be used in the form of an admixture in which a known and publicly available additive for a hydraulic composition is appropriately adopted and combined according to various uses. Specifically, conventionally known cement dispersants, high-performance AE water reducing agents, high-performance water reducing agents, AE water reducing agents, water reducing agents, air entraining agents (AE agents), foaming agents, defoaming agents, coagulation delaying agents, At least one other additive selected from the group consisting of a coagulation accelerator, a separation reducing agent, a thickening agent, a shrinkage reducing agent, a curing agent, a water repellent and the like can be blended.
The dispersant for a water-hard composition containing the polycondensation product or copolymer of the present invention is a form composed of the polycondensation product or copolymer of the present invention described above, or the polycondensation product of the present invention or the copolymer. A form in which a copolymer and other publicly known admixtures are blended to form an admixture for a water-hard composition, or when a water-hard composition such as concrete is produced, the above-mentioned polycondensation product or copolymer is publicly used. Includes any of the forms in which the admixtures of are added separately and finally mixed in the water-hard composition.

Generally, cement dispersants are appropriately combined and used according to concrete production conditions, performance requirements, and the like. The same applies to the cement dispersant of the present invention, which is used alone or as a main agent as a cement dispersant, but as a reforming aid for a cement dispersant having a large slump loss or as an initial water reducing agent. It can be used in combination as a high cement dispersant.
Known cement dispersants include salts of polycarboxylic acid-based copolymers described in Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, etc., and naphthalene sulfonic acid formarin condensates. Salt, salt of melamine sulfonic acid formalin condensate, lignin sulfonate, sodium gluconate, sugar alcohol can also be mentioned. The compounding ratio of the polycondensation product or copolymer of the present invention to the known cement dispersant is, for example, 1:99 to 99: 1% by mass.

Specific examples of the air entraining agent include anionic air entraining agent, nonionic air entraining agent, and amphoteric air entraining agent.
Examples of the setting retarder include an inorganic setting retarder and an organic setting retarder.
Examples of the accelerator include an inorganic accelerator and an organic accelerator.
Examples of thickeners / separation reducing agents include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymers, and nonionic thickeners.
Examples of defoaming agents include nonionic defoaming agents, silicone-based defoaming agents, higher alcohols, and mixtures containing these as main components.

When the dispersant for a water-hardening composition of the present invention is applied to, for example, a cement composition, the components constituting the cement composition are conventionally conventional components for concrete, and cement (for example, ordinary Portland cement, early strength) is used. Portland cement, ultra-fast-strength Portland cement, low-heat / moderate-heat Portland cement or blast furnace cement, etc.), aggregates (ie, fine aggregate and coarse aggregate), admixtures (eg silica fume, calcium carbonate powder, blast furnace slag fine powder, frying) (Ash, etc.), expansion material and water can be mentioned.
Further, as an admixture other than the dispersant for the hydraulic composition of the present invention, which can be added separately at the time of preparation, the above-mentioned publicly known air entraining agent, coagulation retarder, accelerator, separation reducing agent, thickener, etc. There are antifoaming agents, shrinkage reducing agents and the like, and these can also be appropriately blended. The blending ratio of each of these components can be appropriately determined according to the type of selected component and the purpose of use.

The amount of the dispersant for a hydraulic composition of the present invention varies depending on the compounding conditions including the above-mentioned concrete material, but when the amount of the cement is increased or when a fine powder of pozzolanate such as fly ash is used in combination. About 0.05 to 5.0% by mass is usually added in terms of solid content with respect to the total mass of cement and fly ash. In order to obtain water reduction and slump flow retention, it is better to add a large amount, but if it is too large, condensation delay may occur, and in some cases, curing failure may occur.
The method of use is the same as that of a general cement dispersant, and the undiluted solution is added at the time of concrete kneading, or it is diluted in advance with kneading water and added. Alternatively, concrete or mortar may be kneaded and then added, and then uniformly kneaded again.

The present invention will be described below with reference to Examples. However, the present invention is not limited to these Examples and Comparative Examples.

In the examples, the physical properties of the sample were measured using the following devices under the following conditions.
(1) GPC (Gel Permeation Chromatography)
<Gel permeation chromatography (GPC) measurement conditions>
Columns: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko KK)
Eluent: A mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80/20)
Detector: differential refractometer, calibration curve: polyethylene glycol

[Example 1: Preparation of (A)]
<EO adduct: used in polycondensation products of Examples 1 to 17 and 19>
A stainless steel high-pressure reactor equipped with a thermometer, agitator, a pressure gauge, and a nitrogen introduction tube was charged with 100 parts of ortho-hydroxyethylphenol (Aldrich's reagent) and 0.3 parts of 96% potassium hydroxide in the reaction vessel. Was replaced with nitrogen and heated to 130 ° C. in a nitrogen atmosphere. Then, 190 parts of ethylene oxide was introduced into the reactor in 4 hours while maintaining 130 ° C. under safe pressure, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, and the total amount of ortho-hydroxyethylphenol. A 6 molar EO adduct was obtained.
Following this procedure, the number of moles of ethylene oxide adduct was varied to prepare various EO adducts of hydroxyethylphenol shown in Table 1 described later.
<Phosphate ester derivative: used in the polycondensation product of Example 18>
In a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 3 mol of an EO adduct of ortho-hydroxyethylphenol (6 mol adduct in total) was charged, and 1 mol at 50 ° C. while performing nitrogen bubbling. The anhydrous phosphoric acid of No. 1 was charged and reacted over 4 hours. Then, the aging reaction was carried out at 100 ° C. for 3 hours to terminate the phosphoric acid esterification reaction, and an ortho-hydroxyethylphenol EO adduct phosphoric acid ester was obtained.
<Sulfate ester derivative: used in the polycondensation product of Example 20>
In a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 1 mol of an EO adduct of ortho-hydroxyethylphenol (6 mol adduct in total) was charged, and 1 mol at 40 ° C. under a nitrogen atmosphere. Chlorosulfuric acid was charged over 3 hours and a sulfate reaction was carried out. Then, it was dehydrochlorinated by nitrogen bubbling for 1 hour to obtain an acidic compound.
Separately from the above, a glass reaction vessel equipped with a stirrer and a thermometer was prepared, and 1 mol of 48% sodium hydroxide solution and 4.5 mol of water were charged. The entire amount of the acidic compound obtained by the sulfate reaction was charged into this alkaline aqueous solution at 40 ° C. for 3 hours to carry out a neutralization reaction. In this process, the pH was adjusted by appropriately adding a 48% sodium hydroxide solution so that the pH became 7. In this way, an aqueous solution of ortho-hydroxyethylphenol EO adduct sulfate (active ingredient (solid content concentration) 28%) was obtained.

[Example 2: Preparation of (B)]
80 parts of diethylene glycol monophenyl ether (High Solve DPH manufactured by Toho Kagaku Kogyo Co., Ltd.) and 0.2 parts of 96% potassium hydroxide in a stainless steel high-pressure reactor equipped with a thermometer, agitator, pressure gauge, and nitrogen introduction tube. The mixture was charged, the inside of the reaction vessel was replaced with nitrogen, and the mixture was heated to 150 ° C. in a nitrogen atmosphere. Then, 1700 parts of ethylene oxide was introduced into the reactor under safe pressure at 150 ° C. for 10 hours, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction to complete the polyethylene glycol monophenyl ether (EO). The number of added moles = 90) was obtained.
Following this procedure, the number of moles of ethylene oxide added was varied to prepare various polyethylene glycol monophenyl ethers shown in Table 1 described later. The 6 molethylene oxide adduct of phenol (see No. 15) was prepared according to the above synthesis procedure except that the starting material was phenol. As the 1 molar ethylene oxide adduct of phenol (see No. 16), High Solve EPH manufactured by Toho Chemical Industry Co., Ltd. was used.

[Example 3: Preparation of (C)]
<Preparation of EO adduct>
Phenol, p-tert-butylphenol (manufactured by DIC Corporation, PTBP), or p-octylphenol (manufactured by DIC Corporation, POP) is used as a starting material, and ethylene oxide is added according to the preparation method (A) above. The reaction was carried out. The number of moles of ethylene oxide added was q as shown in Table 1.
<Phosphate esterification and sulfate esterification>
The phosphate esterification and the sulfate esterification were carried out according to the phosphoric acid esterification procedure and the sulfate esterification procedure of (A), except that only the type of starting material was changed.

[Preparation Example 1: Preparation of polycondensation product of Example 1]
Each of the raw materials (A) to (C) was charged in a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser at the molar ratio shown in Table 1. This was heated to 70 ° C., and then 98% sulfuric acid was charged in an amount of 1.0 wt% based on the total weight of (A) to (C). Next, the raw materials (D) were collectively charged into the reaction vessel at the molar ratio shown in Table 1, and then the temperature was raised to 105 ° C. When reaching 105 ° C, the pH of the reactants was 2.1 (1% aqueous solution, 20 ° C). The reaction was terminated 6 hours after reaching 105 ° C., 48% caustic soda was charged, and neutralization was performed so that the pH of the 1% aqueous solution of the reaction product was in the range of 5.0 to 7.5. Then, an appropriate amount of water was added so that the solid content of the reaction product was 40%, and an aqueous solution of the polycondensation product was obtained. GPC measurement was performed on this polycondensation product to determine the weight average molecular weight.
[Preparation Examples 2 to 20: Preparation of polycondensation products of Examples 2 to 20]
Following the procedure of Preparation Example 1, the raw material types and molar ratios (A) to (D) were changed as shown in Table 1 to obtain an aqueous solution of each polycondensation product.

[Comparative Preparation Example 1: Preparation of Polycondensation Product of Comparative Example 1]
The polycondensation product of Comparative Example 1 was prepared according to the following procedure disclosed in Japanese Patent No. 5507809 (paragraph [0049] [Preparation of polycondensation product of the present invention B.1].
First, 1 mol of poly (ethylene oxide) monophenyl ether (1000 g / mol), 2 mol of phenoxyethanol phosphate (or a mixture of 2-phenoxyethanol dihydrogen phosphate and 2-phenoxyethanol hydrogen phosphate), 16.3 mol of water, And 2 mol of H ₂ SO ₄ was placed in a reaction vessel and stirred. 3 mol of formaldehyde in the form of a 37% aqueous solution was added dropwise to the solution thus formed. The polycondensation reaction was completed at 105 ° C. for 5 hours. After completion of the reaction, a 20% aqueous NaOH solution was used to bring the pH of the reaction mixture to 10.5. After an additional 30 minutes at 105 ° C., the mixture was cooled to room temperature and water was added to adjust the solids to about 30% by weight.
In the polycondensation product of Comparative Example 1 thus obtained, the weight average molecular weight Mw measured by gel permeation chromatography was 22,000.

[Comparative Preparation Example 2: Preparation of Polycondensation Product of Comparative Example 2]
The polycondensation product of Comparative Example 2 was prepared according to the following procedure (paragraph [0069] [Example 1.1]) disclosed in Japanese Patent Application Laid-Open No. 2014-503667.
First, 2-phenoxyethanol (96%, 16.92 g) was added to a reactor equipped with a jacket and mechanical impeller set at 70 ° C. Polyphosphoric acid (80% in P ₂ O ₅ , 9.60 g) was added to the reactor with stirring 2-phenoxyethanol. The mixture was stirred at 80 ° C. for 30 minutes, followed by the supply of polyoxyethylene monophenyl ether (96%, Mn = 5000 g / mol, 200 g). The mixture was then heated to 100 ° C. Concentrated sulfuric acid (96%, 6.10 g), formalin (37%, 9.36 g) and paraformaldehyde (94%, 1.92 g) are added to the mixture and the mixture is heated to 110-115 ° C. , And stirred for 2 hours. The mixture was then cooled to 60 ° C. and 32% by weight aqueous sodium hydroxide solution was added to neutralize the mixture to pH 9.1.
In the polycondensation product of Comparative Example 2 thus obtained, the weight average molecular weight Mw measured by gel permeation chromatography was 22,000.

[Test I: Fresh mortar test]
<Mortar combination>
500 g of ordinary Portland cement manufactured by Pacific Cement Co., Ltd. or 500 g of the cement and fly ash in total, 1350 g of fine aggregate or fine aggregate and clay, etc. [Clay (collected fine particles) or clay (bentonite, kaolinite)] 1350 g, as a dispersant for a water-hard composition, the above-mentioned polycondensation products 1 to 20 or the polycondensation products 1 to 2 of the comparative example Using 225 g of ion-exchanged water [water / cement ratio (mass ratio) = 0.45] containing [mass%, 0.20 mass%, or 0.22 mass% addition (see Table 2)], the procedure described later Mortar was prepared (see Mortar Formulation in Table 2).

The clay (collected fine particles) used in this test is the collected fine particles obtained by collecting components of 75 μm or less from Futtsu mountain sand, and the clay (collected fine particles) with a nominal size of 75 μm specified in JIS Z 8801-1 is used as clay (collected fine particles). Used as collected fine particles).
As clay, the following commercially available products were used.
Bentonite: Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Kaolinite: RC-1 (manufactured by Takehara Chemical Industry Co., Ltd.)

<Fresh mortar test>
In accordance with the provisions of JIS R 5201, Formulation No. shown in Table 2 A fresh mortar test was carried out using the mortars of Formulations A to E prepared according to (1) to (5), respectively.
Specifically, kneading water (ion-exchanged water) prepared by adding a dispersant for a water-hard composition (polycondensation products 1 to 20 or polycondensation products 1 to 2 of Comparative Example) in advance is added to powder (ion exchange water). In addition to cement or cement and fly ash) and sand (fine aggregate, or fine aggregate and clay, etc.), knead at low speed for 40 to 60 seconds using a high power mixer (manufactured by Maruto Seisakusho Co., Ltd.). It was mixed and allowed to stand for 30 seconds. The kneading time was appropriately selected as a time during which it was confirmed that the mortar was in a fluid state from the start of kneading (the kneading time common to the formulations A to E). The mortar adhering to the wall of the container was scraped off in 20 seconds from the start of standing, and after the end of the standing period, the mixture was kneaded at high speed for 90 seconds to prepare a test mortar.
For the mortar used in the test, in order to avoid the influence of air bubbles in the mortar on the fluidity of the mortar, a defoaming agent (Pronal 753W manufactured by Toho Chemical Industry Co., Ltd.) was used, and the total mass of cement or cement and fly ash was used. The amount of air was adjusted by using the amount of 0.01 wt%.

<Measurement of mortar flow and calculation of liquidity retention rate and liquidity volatility>
Regarding the test mortar immediately after kneading and the test mortar after 30 minutes have passed, a mini slump cone (upper end inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) conforming to JIS A 1171 "Test method for polymer cement mortar". ) Was used to measure the spread (flow value) of the mortar.
The results obtained are shown in Table 3.

With respect to the test mortars of Formulation A, Formulation C and Formulation E, the rate of change of the flow value immediately after kneading and the flow value after 30 minutes had passed as the fluidity retention rate was calculated by the following formula.
Liquidity retention rate (%) = [Flow value after 30 minutes / Flow value immediately after kneading] x 100
The results obtained are shown in Table 3.

In addition, for test mortars with the same dispersant for hydraulic composition (and the amount used thereof), clay or clay or clay or mortar without clay (blended A mortar) has a flow value as a fluidity fluctuation rate. The rate of change in the flow value of the mortar (formulation B to formulation E) when clay was added was calculated by the following formula. It can be evaluated that the closer the fluidity volatility (%) is to 100%, the better the result is that the change in fluidity due to the inclusion of clay or clay is small.
Liquidity volatility (%) = [Flow value when clay or clay is added (blending B to E) / Flow value when clay or clay is not added (blending A)] x 100
The results obtained are shown in Table 3.

<Measurement of curability (exothermic peak)>
The test mortar prepared in Formulation A was filled in a plastic container having a diameter of 10 cm and a height of 12 cm, placed in the center of a simple heat insulating box made of urethane foam, and K-type thermocouple manufactured by Kyowa Electric Co., Ltd. The internal temperature of the mortar was measured using a wire diameter (0.1 mm) and NTB-201A.
Then, from the history of the internal temperature of the mortar, the time to reach the maximum temperature (heat generation peak time: minutes (h: m)) was confirmed.
The results obtained are shown in Table 3.

<Evaluation of the appearance of the cured mortar>
Following the procedure of the previous <Fresh mortar test>, the test mortar prepared in Formulation E was filled in a triple mold manufactured by Maruto Seisakusho Co., Ltd., and after 24 hours, it was demolded to obtain a cured mortar. ..
The cured mortar obtained by the above procedure was photographed on the casting surface (4 cm × 16 cm), and the casting surface (surface photograph) was divided into 1 square 5 mm × 5 mm, for a total of 256 squares. The blackhead area ratio (rounded to the first decimal place) was calculated by counting the number of squares in which darkening occurred among the 256 squares, and the appearance (blackening) was evaluated according to the following criteria.
Evaluation 1: Darkened area ratio on the surface of the cured product = 5.0% or more 2: Darkened area ratio on the surface of the cured product = 3.0 to 4.9%
3: Darkened area ratio on the surface of the cured product = 1.0 to 2.9%
4: Darkening area ratio on the surface of the cured product = less than 1.0% The results obtained are shown in Table 3.

As shown in Table 3, when the formulation A is compared with the formulation B, the formulation C and the formulation D, the hydraulic composition dispersant containing the polycondensation product of the present invention contains clay (formulation B) in the fine aggregate. ), Bentonite (formulation C) or kaolinite (formulation D) are mixed, and it is confirmed that the mortar flow value fluctuates less and high fluidity can be maintained as compared with the formulation A which does not contain these clays and the like. ..
Further, as the formulation E, even when fly ash is used as the hydraulic powder in the formulation in which bentonite is mixed, the fluctuation of the mortar flow value is small, and the flow value is maintained even after 30 minutes, and the fluidity is retained. It was also confirmed that it was excellent in the above, and further, it was confirmed that the darkening of the appearance of the cured product was suppressed as compared with the hydraulic composition dispersant containing the polycondensation product of the comparative example.
On the other hand, the water-hard composition dispersant containing the polycondensation products of Comparative Example 1 and Comparative Example 2 prepared from a monomer mixture containing no compound corresponding to compound A (alkylene oxide adduct of hydroxyethylphenol). As a result, the mortar flow value fluctuated (decreased) greatly due to the blending of clay and clay, and the flow value after 30 minutes also dropped significantly. In addition, in the system using fly ash together, the darkening of the surface of the cured product was conspicuous.

More specifically, by increasing the proportion of compound A (alkylene oxide adduct of hydroxyethylphenol) in the monomeric mixture, the mortar flow value fluctuates, especially in the case of clay (formulation B) and bentonite (formulation C). It was confirmed that the number can be reduced (see Example 10, Example 6, and Example 11).
Further, in Compound A, it was confirmed that the water reduction was improved as the average number of moles of ethylene oxide added was increased, and that the same degree of water reduction could be secured even if the addition amount was reduced by 10% (Example 13, Example 1, See Example 14).
Then, in compound A, the terminal OH is an ester derivative anionized with a phosphoric acid ester group or a sulfuric acid ester group to shorten the kneading time, that is, a uniform state of various materials such as cement and sand in a short time. It was confirmed that it can be mixed with the above, and that the phosphate ester group is particularly effective (see Example 1, Example 18, and Example 20).

Further, in compound B (an alkylene oxide adduct of phenol or a derivative thereof), the water reduction is improved as the average number of moles of ethylene oxide added is increased, and the same degree of water reduction can be ensured even if the addition amount is reduced by 10%. It was confirmed (see Example 3, Example 1, and Example 2).
Further, it was confirmed that when two or more kinds of compound B are used in combination, the retention property is improved and the resistance to clay (bentonite / kaolinite) is further improved (Example 1, Example 15, Example 16). reference).

Further, in compound C (phosphate ester or sulfate ester derivative of phenol alkylene oxide adduct), by alkyl-substituting the benzene ring, the fluidity at the time of FA compounding is improved and the appearance of the cured product is good. The result was obtained. Further, it was confirmed that the appearance of the cured product was further improved by increasing the chain length of the substituted alkyl group (Example 1, Example 6, Example 9).
Further, it was confirmed that the fluidity at the time of blending fly ash was improved by increasing the proportion of compound C in the monomer mixture, and it was confirmed that the water reduction and retention could be adjusted by adjusting the proportion of compound C. (Example 7, Example 6, Example 8).
Then, in the anionization of the terminal of Compound C, the phosphoric acid ester has a higher water-reducing property than the sulfate ester, while the sulfate ester does not reach the phosphoric acid ester even if the addition amount is increased by 10%. (See Example 18 and Example 20).

[Test II: Concrete test]
<Concrete composition>
The concrete compounding No. shown in Table 4. 1 and formulation No. 2 In each of 2, the mixing water (ion-exchanged water) prepared by adding the polycondensation products (Examples 1 to 3, 6, 15, 16, 19) and the water reducing agent in the addition amounts shown in Tables 5 and 6 in advance. Was used to prepare fresh concrete in accordance with JIS A 1138. As the water reducing agent, a commercially available AE water reducing agent (high-performance type, containing lignin sulfonate) and the admixture C-1 described in Examples of Japanese Patent No. 2774445 were used. As shown in Tables 5 and 6, concrete containing a dispersant for a hydraulic composition containing only a water reducing agent without containing the polycondensation product of Examples was used for the comparative test.
As a kneading method, a biaxial forced kneading mixer having a nominal capacity of 100 liters was used, and the amount of concrete produced in each batch was 50 liters x 1 batch.
First of all, cement, fly ash, fine aggregate, mixed water, coarse aggregate and water reducing agent are added and compounded No. In No. 1, compounding No. 1 was used for 90 seconds. In No. 2, kneading was performed for 120 seconds.

<Concrete test>
For various concretes produced by the above procedure, slump, slump flow, 50 cm flow arrival time, and flow stop time were measured at 0 to 30 minutes over time in accordance with JIS A 1101 and JIS A 1150. After measuring the slump flow, a sample was collected in a summit mold of φ15 cm × 30 cm, vibrated using a table vibrator for 60 seconds, and then the appearance of the upper surface of the test piece was observed. In addition, the same sample was used to measure the amount of air in accordance with JIS A 1128.
In addition, the setting time of concrete was measured according to JIS A 1147. The temperature of the fresh concrete used in the above test was 20 ± 3 ° C.
Formulation No. The results for the concrete of No. 1 are shown in Table 5, and the compounding No. Table 6 shows the results for the concrete of 2.

As shown in Tables 5 and 6, Formulation No. 1 and formulation No. Test Examples 1 to 7 and Test Examples 8 to 8 containing the dispersant for the hydraulic composition of the present invention ((polycondensation products 1-3, 6, 15, 16, 19) and water reducing agent) in the concrete of 2. The concrete of 14 has better stability over time, lower concrete viscosity, and less condensation delay than the concrete of Comparative Test Example 1 and Comparative Test Example 2 containing only a water reducing agent, so that the workability is also good. Further, the water reduction can be maintained in a high state even when it is blended with a concrete composition containing fly ash (FA), and in particular, unburned carbon floats on the surface of concrete in a cured product of the FA blended composition. It is possible to suppress the occurrence of darkening of the surface caused and provide a cured product having an excellent appearance.

Claims (6)

It contains compound A represented by the following formula (A), compound B represented by formula (B), compound C represented by formula (C), and one or more aldehyde compounds D represented by formula (D). A polycondensation product containing a copolymer obtained by polycondensing a monomer mixture.

(During the ceremony,
A ₁ O and A ₂ O each independently represent an alkylene oxide group having 2 to 4 carbon atoms.
m is an average addition number of moles of alkylene oxide, a number from 0 to 300, n is an average addition number of moles of alkylene oxide, a number from 1 to 300, a and m + n ≧ 1,
A ₃ O represents an alkylene oxide group having 2 to 4 carbon atoms.
p is the average number of moles of alkylene oxide added and represents a number from 1 to 300.
X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.
A 4 _O represents an alkylene oxide group having 2 to 4 carbon atoms,
q is the average number of moles of alkylene oxide added and represents a number from 1 to 300.
R ₀ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms.
R ₁ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms.
Y ₁ and Y ₂ independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group, respectively.
Y ₃ represents a phosphoric acid ester group or a sulfuric acid ester group,
R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group,
r represents a number from 1 to 100. ) The monomer mixture
The compound A, the compound B and the compound C are contained in a molar ratio of compound A: compound B: compound C = 0.1 to 2: 0.1 to 2: 0.1 to 4 and
Compound D is contained in a molar ratio of (Compound A + Compound B + Compound C): Compound D = 1 to 10: 10 to 1 with respect to the total molar amount of Compound A, Compound B and Compound C.
The polycondensation product according to claim 1. The polycondensation product according to claim 1 or 2, wherein the monomer mixture comprises two or more kinds of compounds B represented by the formula (B). The polycondensation product according to any one of claims 1 to 3, wherein the monomer mixture contains two or more kinds of compounds C represented by the formula (C). A dispersant for a hydraulic composition containing the polycondensation product or copolymer according to any one of claims 1 to 4. The compound A represented by the formula (A) according to claim 1, the compound B represented by the formula (B) according to claim 1, the compound C represented by the formula (C) according to claim 1, and the claim. A copolymer obtained by polycondensing a monomer mixture containing one or more aldehyde compounds D represented by the formula (D) described in 1.